EP0014167B1 - Aniline derivatives with antifungal activity and process for their preparation - Google Patents

Description

The present invention relates to new sulfur products containing an amide group amide. The invention also relates to the preparation of said products and their application for the protection of plants, especially against fungi and fungal diseases.

It is already known (patent FR-A 7510722) fungicidal compounds derived from N-acyl N-aryl amino acids. However, it is desirable to have a wide range of fungicide products of different formulas. Indeed, the qualities of different pesticides are rarely identical to each other so that it is better to have a large number of products if you want to deal with all cases of attacks against plants.

dans laquelle

• R' et R⁵, identiques ou différents, représentent un radical alkyle ou alkoxyle ayant de 1 à 4 atomes de carbone ou un atome d'halogène ou l'atome d'hydrogène, un seul des deux radicaux R' ou R⁵ pouvant avoir cette dernière signification,
• R², R³ et R⁴, identiques ou différents, représentent l'atome d'hydrogène ou un atome d'halogène ou un radical alkyle ou alkoxyle ayant de 1 à 4 atomes de carbone,
• R⁶ représente l'atome d'hydrogène ou un radical méthyle,
• R⁷ représente l'atome d'hydrogène ou un radical alkyle ayant de 1 à 12 atomes de carbone ou 1/n Mⁿ⁺, M étant un cation de valence n, plus particulièrement un cation d'ammonium (éventuellement substitué) ou un cation métallique,
• R⁸ représente l'atome d'hydrogène ou un radical de formule R^9--CO- dans laquelle R⁹ est un radical organique qui représente
  • - un radical alkyle ou alkényle, linéaire ou ramifié, ayant au plus 18 atomes de carbone et pouvant être substitué par des atomes d'halogènes ou des groupements hydroxy, mercaptan, cyano, oxo ou des radicaux alkyloxy, alkylthio, aryle, alkoxycarbonyle, acylamino, ces divers radicaux ayant au plus 6 atomes de carbone.
  • - un radical cycloalkyle comportant 3 à 7 atomes de carbone dans le cycle (de préférence les radicaux cyclopropyle, cyclopentyle, ou cyclohexyle) et pouvant être substitué par des atomes d'halogène ou des groupements alkyle ayant au olus 4 atomes de carbone.
  • - un radical phényle ou naphtyle éventuellement substitué par des atomes d'halogène ou des groupements alkyle, ou acyloxyle, acyle, alkoxyle, ces divers groupements ayant au plus 6 atomes de carbone.
  • - un radical hétérocyclique comportant, dans le cycle, 5 ou 6 atomes dont 1 à 3 sont des hétéroatomes d'oxygène, d'azote ou de soufre, ce radical hétérocyclique pouvant être substitué par des atomes de chlore ou des groupements méthyle ou éthyle, et la valence libre de ce radical R⁹ (c'est-à-dire la valence rattachée au groupe carbonyle dans le radical R9-CO-) étant porté par un atome de carbone.
  • - un radical comprenant un groupe hétérocyclique ayant la même signification que celle indiquée dans le paragraphe précédent, ce groupe hétérocyclique étant relié au groupe carbonyle (de R^9-CO-) par l'intermédiaire d'un radical divalent méthylène ou éthylène.

The compound products according to the invention are characterized in that they have the formula

in which

• R 'and R ⁵ , identical or different, represent an alkyl or alkoxyl radical having from 1 to 4 carbon atoms or a halogen atom or the hydrogen atom, only one of the two radicals R' or R ⁵ may have this last meaning,
• R ² , R ³ and R ⁴ , identical or different, represent the hydrogen atom or a halogen atom or an alkyl or alkoxyl radical having from 1 to 4 carbon atoms,
• R ⁶ represents the hydrogen atom or a methyl radical,
• R ⁷ represents the hydrogen atom or an alkyl radical having from 1 to 12 carbon atoms or 1 / n M ^{n +} , M being a cation of valence n, more particularly an ammonium cation (optionally substituted) or a cation metallic,
• R ⁸ represents the hydrogen atom or a radical of formula R ^9-- CO- in which R ⁹ is an organic radical which represents
  • - a linear or branched alkyl or alkenyl radical having at most 18 carbon atoms and which may be substituted by halogen atoms or hydroxy, mercaptan, cyano, oxo groups or alkyloxy, alkylthio, aryl, alkoxycarbonyl, acylamino radicals , these various radicals having at most 6 carbon atoms.
  • a cycloalkyl radical containing 3 to 7 carbon atoms in the ring (preferably the cyclopropyl, cyclopentyl, or cyclohexyl radicals) and which can be substituted by halogen atoms or alkyl groups having at least 4 carbon atoms.
  • - a phenyl or naphthyl radical optionally substituted by halogen atoms or alkyl, or acyloxyl, acyl, alkoxyl groups, these various groups having at most 6 carbon atoms.
  • a heterocyclic radical comprising, in the ring, 5 or 6 atoms of which 1 to 3 are heteroatoms of oxygen, nitrogen or sulfur, this heterocyclic radical may be substituted by chlorine atoms or methyl or ethyl groups, and the free valency of this radical R ⁹ (that is to say the valence attached to the carbonyl group in the radical R9-CO-) being carried by a carbon atom.
  • a radical comprising a heterocyclic group having the same meaning as that indicated in the previous paragraph, this heterocyclic group being linked to the carbonyl group (of R ^9- CO-) via a divalent methylene or ethylene radical.

The substitution of a radical by an oxo group (that is to say by = O), corresponds, according to the usual terminology, to the presence of a carbonyl group ―CO― in this radical.

Among the halogen atoms which may appear in the substances represented by formula (I), use may in particular be made of chlorine and bromine.

représente donc un groupe carboxylique ou carboxylate, la liaison o-R⁷ pouvant être soit de type covalent (notamment dans le cas où ―COO―R⁷ représente un groupe ester) soit de type ionique (notamment dans ie cas où ―CCO―R⁷ représente un groupement salin) soit des deux types (notamment dans le cas de -COOH qui peut être ionisé ou non ionisé, ou partiellement ionisé).According to the definition given above, the group

therefore represents a carboxylic or carboxylate group, the oR ⁷ bond being either of the covalent type (especially in the case where ―COO ― R ⁷ represents an ester group) or of the ionic type (especially in the case where ―CCO ― R ⁷ represents a salt group) or of two types (especially in the case of -COOH which can be ionized or non-ionized, or partially ionized).

dans laquelle R^l, R², R³, R⁴, R⁵, R⁶, R⁸, M et n ont les significations données précédemment.When the group ―COO ― R ⁷ represents a salt group, it has been indicated that R ⁷ can then have the meaning 1 / n M ^{n +} M being a cation of valence n; the group ―COO ― R ⁷ can, in this case also be represented in ia form (more formally exact) ―COO ^⊖ , 1 / n M ^{n +} ; but this is also a medium formula; the even more correct (but in reality equivalent) representation of the molecule of formula (I) is then

in which R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁸ , M and n have the meanings given above.

In the general family of compounds of formula (I) as just defined, a particular subfamily is especially advantageous; it has in particular very good antifungal properties especially with regard to phycomycetes, and more particularly with regard to downy mildew.

• R² représente un atome d'hydrogène, de chlore ou de brome
• R³ et R⁴ représentent l'atome d'hydrogène
• R' et R⁵ représentent un groupe alcoyle ayant de 1 à 4 atomes de carbone
• R⁶ est l'atome d'hydrogène ou le groupe méthyle
• R⁷ est un groupe alkyle de 1 à 4 atomes de carbone, et plus spécialement le radical méthyle.

These preferred products are such as:

• R ² represents a hydrogen, chlorine or bromine atom
• R ³ and R ⁴ represent the hydrogen atom
• R 'and R ⁵ represent an alkyl group having from 1 to 4 carbon atoms
• R ⁶ is the hydrogen atom or the methyl group
• R ⁷ is an alkyl group of 1 to 4 carbon atoms, and more especially the methyl radical.

• R⁶ représente l'atome d'hydrogène ou un radical R^9--CO-
• R⁹ représente
  • - un radical alkyle ou alkényle éventuellement substitués par des atomes de chlore ou des groupes alkoxyle ayant de 1 à 4 atomes de carbone ou des groupes cyano, oxo, acétamido, phényle, chlorophényle, alkylthio, alkoxycarbonyle
  • - un radical cyclopropyle, cyclopentyle ou cyclohexyle
  • - un radical phényle éventuellement substitué par un atome de chlore ou de brome
  • - un radical hétérocyclique furyle, thiényle, trichlorothiényle ou pyridyle.

In these families thus defined, the compounds in the formula of which are also preferred

• R ⁶ represents the hydrogen atom or a radical R ^9-- CO-
• R ⁹ represents
  • - an alkyl or alkenyl radical optionally substituted by chlorine atoms or alkoxyl groups having from 1 to 4 carbon atoms or cyano, oxo, acetamido, phenyl, chlorophenyl, alkylthio, alkoxycarbonyl groups
  • - a cyclopropyl, cyclopentyl or cyclohexyl radical
  • - a phenyl radical optionally substituted by a chlorine or bromine atom
  • - a heterocyclic furyl, thienyl, trichlorothienyl or pyridyl radical.

The products in which R ¹ , R ⁵ and R ⁷ are the methyl radical and R ⁹ is an alkyl radical having from 1 to 9 carbon atoms are very particularly advantageous.

The compounds according to the invention (of formula I) can be prepared according to several methods.

Some of the processes which can be used are designated respectively below by the letters (A), ( _B ), (C), (D) and correspond to the following reaction schemes:

According to the first method, or method (A), a compound of formula (III) is obtained by reaction of an N-phenylamino acid derivative of formula (IV) with an acid chloride of formula (V), the symbols R 'to R ⁶ and R ⁶ and R ⁹ having the meanings given above and the symbol R ⁷ representing the hydrogen atom or an alkyl radical.

The reaction used in this process (A) is advantageously carried out in solution in an inert solvent (that is to say one which does not react chemically with the reagents under the operating conditions). The reaction temperature is generally higher than 40 ° C and lower than the degradation temperature of the reactants and / or reaction products. The temperature is thus generally between 60 and 150 ° C. According to a convenient method, the operation is carried out at the boiling point of the solvent in question. As suitable solvent, there may be mentioned polar or "non-polar aprotic organic solvents. It is preferred to use solvents whose boiling point is included in the zone indicated for the reaction temperature; they may therefore be aromatic hydrocarbons ( such as benzene, toluene, xylenes, chlorobenzene) or aliphatics (such as hexane, heptane, cyclohexane, methylcyclohexane), or chlorinated aliphatic hydrocarbons (such as dichloroethane, dichloroethylene , chloroform, carbon tetrachloride) or ethers (such as dioxane, tetrahydrofuran, diethyl ether) or ketones (such as acetone, methyl ethyl ketone, methylisobutyl ketone) or nitriles (such than acetonitrile).

The reaction can be catalyzed, for example by dimethylformamide; it can be carried out in the absence or in the presence of a condensing agent, in particular an acid acceptor. As acid acceptors, tertiary amines such as trialkylamines (for example triethylamine) or N-aryldialkylamines (for example N, N-dimethylaniline) or alternatively pyridine and pyridine bases or inorganic bases such as carbonates and hydrogen carbonates of alkali or alkaline earth metals, and sodium acetate. It is also possible to use, as acid acceptor, an excess of the amino compound of formula (IV) and this is a preferred operational method.

It is possible to carry out the reaction in the presence of an excess of either of the reactants. As has just been said, a preferred method however consists in operating in the presence of an excess of compound of formula (IV), at least during the first part of the reaction. It is possible to operate in the presence of an excess of compound of formula (IV) for example by gradually introducing the acid chloride of formula (V) into the reaction medium containing all or part of the compound of formula (IV) which has to be brought into operation. work, then the reaction is continued until the evolution of hydrochloric acid ceases; the amounts of reagents used overall during the reaction are preferably close to stoichiometry; stoichiometry is generally the most advantageous; however, the acid chloride of formula (V) can be used in an amount exceeding stoichiometry, for example up to 10% (by number). At the end of the reaction, the reaction product of formula (III) is isolated by any means known per se, for example by distillation of the solvent (that is to say evaporation) and / or crystallization of the product in the medium.

• J. Org. Chem. 30 p. 4101-4104 (1965)
• Tetrahedron 1967 p. 487-498

As regards the preparation of the compounds of formula (IV), it can be carried out according to methods similar to those described for the preparation of anilino alkanecarboxylic esters in the following publications:

• J. Org. Chem. 30 p. 4101-4104 (1965)
• Tetrahedron 1967 p. 487-498

• - le brevet des États-Unis d'Amérique n° 2 412 700
• - Berichte 46 p. 2104-2107 (1913)
• - Annalen 602 p. 1-14 (1957).

The preparation of the acid chlorides of formula (V) can be carried out in accordance with or similar to many known methods, but especially those described in

• - U.S. Patent No. 2,412,700
• - Berichte 46 p. 2104-2107 (1913)
• - Annalen 602 p. 1-14 (1957).

According to the second method, or method (B), compounds of formula (III) are prepared in which R ′ to R ⁷ and R ⁹ have the meanings given for formula (1); this preparation is carried out by reaction of an N-phenylamino acid derivative of formula (VI) with an alkali or alkaline earth thiocarboxylate (preferably alkaline) derived from a thiocarboxylic acid of formula R9-CO-SH (VII). The ammonium cation is included in the alkaline cations which can be used. These thiocarboxylates can be represented by the formula R ⁹ ―CO ― S ― M '[formula (VII bis)], M' representing the alkali (or ammonium) cation or a half-equivalent of alkaline-earth cation.

The derivatives of formula (VI) can be prepared according to methods identical or similar to those described in English patent 1,445,387.

A convenient means for preparing the alkaline thiocarboxylate obviously consists in reacting a thiocarboxylic acid with an alkaline or alkaline earth derivative, such as an alkali or alkaline earth hydroxide or carbonate. If the reaction is carried out in a solvent, a solution (or optionally a suspension) of the thiocarboxylate of formula (VIIa) can thus be obtained directly.

The preparation of the compound of formula (III) from the compounds of formula (VI) and of the thiocarboxylate is generally carried out in the presence of an inert solvent (that is to say chemically inert with respect to the reactants or reaction products under the operating conditions). The reaction temperature and the solvents which can be used are similar to what has been defined with regard to process (A). As solvents, it is also possible to use amides (such as dimethylformamide) and sulfoxides (such as dimethylsulfoxide).

At the end of the reaction, the alkali or alkaline earth chloride which has precipitated is separated (for example by filtration) and the solvent is evaporated; if necessary, it is possible to carry out usual purifications, such as for example washing with water an organic solution of the compound of formula (III).

According to the third process, or process (C), compounds containing a free mercaptan group of formula (VIII) are prepared by reaction between a compound of formula (III) with an alcohol. When R ⁷ is an alkyl group, an alcohol of formula R ⁷ ―OH is advantageously used; among the alcohols that can be used, methanol is preferred. In the reaction carried out in this process (C), forms an ester (for example of formula R ^e COOR ⁷⁾ so that the reaction is a transesterification in the broad sense. The reaction is preferably carried out in an alcoholic solution (methanol if any) in the presence of an agent (or catalyst) alkali ^(1st variant) or acid (2 ⁸ Alternative). ia reaction temperature is generally between 0 and 120 ° C.

As agent (or catalyst) alkali ^[1st variant of process (C)] is preferred to use an alkali metal alkoxide, such as methoxide (also called methanolate) of sodium or potassium. The amount of alkali alcoholate or methylate used is advantageously close to stoichiometry (at least 90% of stoichiometry) relative to the compound of formula (III) used. We prefer to operate just with stoichiometry; according to a preferred method, an alcoholic solution of the compound of formula (III) is gradually added to an alcoholic solution of alkaline alcoholate. The temperature is advantageously between 10 and 50 ° C. At the end of the reaction, it is acidified or, at least, neutralized using an acid to remove the alkali metal in the form of insoluble salt. The latter is then separated, for example by filtration; the compound of formula (VIII) is obtained by evaporation of methanol. It is of course possible to carry out a purification by the usual methods, for example by washing with water an organic solution of the compound of formula (VIII) followed optionally by recrystallization.

The reaction between an alcohol, methanol for example, and the compound of formula (III) may, as already mentioned, be performed in the presence of an agent or acid catalyst [process variant ^e 2 (C)] , preferably a strong mineral or organic acid, for example hydrochloric, sulfuric, paratoluene sulfbnic acids. The amount of acid catalyst used is advantageously between 0.01 and 1 acid equivalent (which corresponds to 0.01 to 1 ion-g H ⁺ or mole of mono-acid) per mole of compound (III). The reaction is generally carried out above 50 ° C. and up to the boiling point of the reaction medium; practically by simple heating in the presence of the acid catalyst.

At the end of the reaction, the alcohol (methanol if necessary) and the acid catalyst are removed, for example by distillation and, if necessary, it is purified by the usual methods.

According to the fourth method, or method (D), compounds of formula (III) are prepared by reaction of a mercaptan of formula (VIII) with an acid derivative R ⁹ COOH, preferably an acid chloride R ⁹ -CO-Cl ^(1st variant) or an anhydride (R ⁹ -CO) ² O ^(2nd variant).

Reacting a chloride R ⁹ CO-CI acid with a mercaptan of formula (VIII), according to the ^1st embodiment, is generally carried out in the presence of a condensing agent which is most often an acceptor acid (also called basic acceptor); it is usually carried out in an inert organic solvent.

As inert organic solvent, mention may be made of those indicated as desirable in the case of process (A).

As the acid acceptor, it is possible to use organic bases such as tertiary amines such as trialkylamines (for example triethylamine) or N-aryldialkylamines (for example N, N-dimethylaniline), or also pyridine and pyridine bases , or mineral bases such as alkali or alkaline earth carbonates or hydrogen carbonates, or sodium acetate.

The reaction is most conveniently carried out at room temperature, but temperatures of 5 to 60 ° C, preferably 10 to 30 ° C can also be used.

The proportions of the various reagents are advantageously close (at least 90%) to stoichiometry; exact stoichiometry (100%) is preferred.

The reaction is preferably carried out by mixing the acid chloride (optionally in the form of a solution) with a mixture of the compound of formula (VIII) and the acid acceptor (the latter mixture possibly being in the form solution). According to the most advantageous method, the acid chloride is gradually added to the mixture of the two other reagents.

During the reaction, the acid acceptor usually gives rise, along with the acid which forms during the reaction, to a reaction by-product which may be an addition compound, for example a hydrochloride. It may be a reaction by-product which is insoluble or soluble in the medium. At the end of the reaction, this reaction by-product is separated; if this reaction by-product is insoluble, the separation can be carried out for example by filtration or spinning; if this reaction by-product is soluble in the medium, the separation can be carried out for example by washing the reaction medium with water. Either way, the solvent is then removed (generally by evaporation) which leads to the compound of formula (III); it is of course also possible to carry out the usual purifications, for example by washing an organic solution of (III) with water or with acidic aqueous solutions, and / or by recrystallization.

According ia ^2nd process variant (D) reacting an acid anhydride (R ⁹ -CO) ² O with a mercaptan of formula (VIII). According to an advantageous method, the anhydride is prepared in situ by action of a dehydrating agent on R ⁹ COOH acid.

The reaction is most conveniently carried out at temperatures between 10 and 120 ° C, in an inert organic solvent. As solvent which can be used, mention may be made of the solvents which can be used in process (A).

As dehydrating agent, mention may be made of carbodiimides, in particular dicyclohexylcarbodimimide. The amounts of dehydrating agent and of R ⁹ COOH acid are preferably close to stoichiometry (at least 90% of stoichiometry) compared to the mercaptan of formula (VIII).

On a practical level, it is also preferred to gradually add the carbodiimide to a mixture of mercaptan of formula (VIII) and of acid R ⁹ COOH.

During the reaction, a substituted urea is generally formed which is eliminated at the end of the reaction by any means known per se, for example by filtration when this substituted urea is insoluble. The solvent is also removed, for example by evaporation, which leads to the isolation of the compound of formula (III).

Other preparation methods which are particularly suitable for the products according to the invention in salt form can also be used.

These compounds of formula (II) can be prepared for example by saponification of the corresponding esters (products of formula (III) in which R ⁷ is an alkyl radical and R ⁸ is the hydrogen atom), this saponification being carried out for example using alkali or alkaline earth hydroxides. The compounds of formula (II) can also be obtained (especially when R ⁶ represents a radical R ⁹ ―CO―) by reaction of an alkali or alkaline earth hydroxide with a compound of formula (II) in which R ⁷ is the hydrogen atom. It is also possible to use double decomposition reactions between a soluble salt of formula (II) and a soluble mineral salt of the desired cation.

The following examples, given without limitation, illustrate the invention and show how it can be put into practice.

Examples 1 to 10 illustrate the preparation of compounds according to the invention according to the various usable methods described above.

Tables I, II and III give the physical characteristics and the elementary analysis of different products according to the invention prepared according to methods analogous to one or the other of the methods appearing in Examples 1 to 10. When the products obtained were crystallized, their melting point was indicated; when the products were oily, the refractive index (n _D ²⁰ ) measured at 20 ° C. was indicated for the sodium D line.

The pesticidal properties of the products in Tables I, II and III are illustrated in Examples 11 to 14; under the conditions of these examples, no compound tested exhibited phytotoxicity.

In Examples 11 to 14, it is considered that a product exerts total protection against a fungal disease when the protection is at least 95%; protection is considered good when it is at least 80% (but less than 95%), as fairly good when it is at least 70% (but less than 80%), as average when is at least 50% (but less than 70%).

In the present description, the percentages are, unless otherwise indicated and except those relating to yields, percentages by weight. In the case where the percentages are expressed relative to the stoichiometry, these are molar percentages.

Compounds 73 and 80 have been shown in ionic form; it should be understood that they can also be considered to be in the covalent form -COOH.

In the following examples, the structure of all the products obtained was checked by nuclear magnetic resonance spectrography (R.M.N.).

Example 1

In 40 cm ³ of toluene, 10.35 g of N- (2,6-dimethylphenyl) alanine methyl ester, of formula

This solution is heated until boiling. In this solution thus heated to boiling at reflux, a second solution consisting of 20 cm ³ of toluene and 7.63 g of acetylthioacetyl chloride of formula CH ₃ ―CO ― S ― CH ₂ - is gradually added over 10 minutes. CO ― Cl. A release of hydrochloric acid is observed during this operation, and heating is continued until this release of gas is stopped (that is to say for 15 mm). The toluene is then removed by distillation under reduced pressure.

There is thus obtained, with a yield of 100%, the methyl ester of N - [(acetylthio) acetyl] -N- (2,6- dimethylphenyl) alanine which is the compound n ° 1 of the table (I).

Its melting point after recrystallization from ethyl alcohol and the elemental analysis are indicated in Table I.

Example 2

A solution of 19.3 g (0.1 mole) of N- (2,6-dimethylphenyl) alanine in 100 cm ³ of toluene is heated to boiling under reflux. While maintaining the boiling point, a solution consisting of 15.25 g (0.1 mole) of acetylthioacetyl chloride and 20 cm ³ of toluene is gradually added over 15 min. The boiling is then maintained for another 15 min until the evolution of gaseous hydrochloric acid is stopped. Half (by volume) of the solvents in the reaction medium is removed by distillation; cooled to 0 ° C; the precipitate obtained is filtered, washed with 10 cm ³ of hexane, drained and finally dried under vacuum (absolute pressure reduced to 27 millibars) at 20 ° C. 15.5 g (yield: 55%) of N - [(acetylthio) acetyl] -N- (2,6-dimethylphenyl) alanine (compound No. 80) are thus obtained, the melting point and elemental analysis of which are indicated in Table III.

The reaction carried out was:

Example 3

4.18 g of mercaptoacetic acid (CH ₃ CO SH) are poured over 30 min onto a suspension of 2.97 g of sodium carbonate in 30 cm ³ of dimethylformamide. The medium having become homogeneous, 14.17 g of methyl ester of ia N- (2,6-dimethyl-phenyl) -N- (chloroacetyl) alanine of formula:

The mixture is heated for 2 hours at 100 ° C. with stirring. After cooling, the sodium chloride formed is removed by filtration and the dimethylformamide is removed by distillation under reduced pressure. The residual oil is dissolved in 30 cm ³ of water each time; the organic solution thus washed is dried over magnesium sulfate, filtered, then concentrated until dry. The oil obtained, added with 5 cm ³ of ethanol, provides a crystallized precipitate which forms slowly. There is thus obtained, with a yield of 62%, the ester. methyl of N- (2,6-dimethylphenyl) -N - [(acetylthio) acetyl] alanine which is compound n ° 1, the characteristics of which are indicated in table (I).

Example 4

In 70 cm ³ of methanol, 35 g of N- (2,6-dimethylphenyl) -N - [(acetylthio) -acetyl] alanine methyl ester (compound No. 1 of Table (I)) are dissolved.

To this first solution is gradually added over 1 hour, at 30 ° C., a solution of sodium methylate prepared by adding 2.5 g of sodium in 150 cm ³ of methanol.

The reaction medium resulting from the mixture of these two solutions is acidified with 10 cm ³ of an aqueous solution of concentrated hydrochloric acid. The sodium chloride formed is filtered; the filtrate is distilled under vacuum so as to evaporate the methanol; the residue from this evaporation is dissolved in 50 cm ³ of methylene chloride; this solution is washed with water until the washings are neutral and then dried over sodium sulfate. The methylene chloride is then removed by evaporation; the oily residue is intimately mixed with 100 cm ³ of hexane, which gives a crystalline precipitate consisting of the methyl ester of N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alanine, which is compound No. 55 of table (II); this table indicates the melting point and elemental analysis of this compound. This compound was thus obtained with a yield of 82%.

Example 5

323 g (1 mole) of methyl ester of N- (2,6-dimethylphenyl) -N - [(acethylthio) acetyl] alanine or compound No. 1 of table (I), are dissolved in one liter of methanol. 10 cm ³ of concentrated aqueous hydrochloric acid solution are added and the mixture is heated for 5 hours at reflux. The methanol is removed by distillation. The oily residue is crystallized by stirring in petroleum ether. The precipitate is filtered, then dried under absolute pressure reduced to 27 millibars. Obtained, with a yield of 98%, the methyl ester of N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alanine, which is the compound No. 55 in Table (II).

Example 6

In 40 cm ³ of toluene 2.5 g of triethylamine and 7 g of methyl ester of N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alanine are dissolved.

To this solution kept under stirring, a solution of 3.6 g of 3,3-dimethyl butanoic acid chloride in 20 cm ³ of toluene is gradually added over 20 minutes; the temperature increases from a value of 20 ° C to a value of 30 ° C during this addition. The agitation is continued for half an hour; triethylamine hydrochloride is removed by spinning; the remaining toluene solution, resulting from this spinning, is washed with a sodium bicarbonate solution and then with water. The toluene is removed under reduced pressure and an oil consisting of the methyl ester of N- (2,6-dimethylphenyl) -N - [(3,3-dimethylbutanoylthio) acetyl] alanine is then obtained.

This product was obtained with a yield of 84%.

The melting point and the elementary analysis are indicated in table (I).

Example 7

• -14,05 g (0,05 mole) de N-(2,6-diméthylphényi)-N-(mercaptoacétyl) alaninate de méthyle de formule
  
• - 4,25 g (0,05 mole) d'acide cyanacétique
  

In 100 cm ³ of methylene chloride, the following are dissolved:

• -14.05 g (0.05 mole) of methyl N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alaninate of formula
  
• - 4.25 g (0.05 mole) of cyanacetic acid
  

The mixture is stirred at 20 ° C. and a solution of 10.3 g of dicyclohexylcarbodimimide in 50 cm ³ of methylene chloride is gradually added over 15 minutes. Then heated to boiling under reflux for 2 h and then cooled to 0 ° C. The precipitate of dicyclohexylurea is filtered, the solvent is distilled off, 50 cm ³ of diethyl ether is added to the residue and the mixture is cooled to -20 °. The precipitate is filtered and dried. 9 g (51% yield) of N - [(cyanacetylthio) acetyl] -N- (2,6-dimethylphenyl) methyl alaninate (compound No. 48) are obtained, the melting point and the elemental analysis of which are indicated in Table I.

Example 8

• - 70,25 g (0,25 mole) de N-(2,6-diméthylphényl)-N-(mercaptoacétyl) alaninate de méthyle
• - 200 cm³ d'une solution aqueuse de soude 0,125 N.

A solution consisting of:

• - 70.25 g (0.25 mole) of methyl N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alaninate
• - 200 cm ³ of an aqueous sodium hydroxide solution 0.125 N.

Concentration to dryness under reduced pressure.

72.3 g are thus obtained (yield: 100%) of sodium N- (2,6-dimethylphenyl) -N- (mercaptoacetyl) alaninate (compound No. 75), the melting point and elemental analysis of which are indicated in Table (III). The reaction carried out was

Example 9

The mixture is heated to reflux until dissolution (for 2 h) a suspension consisting of 50 cm ³ of water, 0.4 g ( _0.01 mole) of MgO and 6.18 g (0.02 mole) of N - [(acetylthio) acetyl] -N- (2,6-dimethylphenyl) alanine. Cool to 0 ° C. The precipitate is filtered, drained, then dried at 40 ° C under absolute pressure of 27 millibars and in the presence of P ₂ 0 ₅ .

4.6 g (72% yield) of N - [(acetylthio) acetyl] -N- (2,6-dimethylphenyl) magnesium alaninate are obtained, the melting point and the elemental analysis of which are given in table (III). . The reaction carried out was

Example 10

A solution of 2.5 g (0.01 mole) of Cu S0 ₄ in 50 cm ³ of water is gradually added over 15 min and with stirring to a solution consisting of 50 cm ³ of water and 6.62 g (0.02 mole) of sodium N - [(acetylthio) acetyl] -N- (2,6-dimethylphenyl) alaninate. Stirring is continued for another 15 min. The precipitate is filtered, washed with water, wrung out and then dried at 40 ° C. under absolute pressure reduced to 27 millibars in the presence of P ₂ O ₅ .

5.5 g (92% yield) of N - [(acetylthio) acetyl] -N- (2,6-dimethylphenyl) cuanic alaninate (compound No. 84) are thus obtained, the melting point and the elemental analysis of which are indicated in table (III). The reaction carried out was

• N-(2,6-diméthylphényl)-N-[(propionylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényt)-N-[(propionylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(propionylthio) acetyl] glycinate de méthyle
• N-[(propionylthioacetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(propionylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(propionylthio) acetyl] alaninate de méthyle
• N-[(propionylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(butyrylthio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-[(butyrylthio) acetyll-N-(3-chloro-2,6-diméthylphényl) glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(butyrylthio) acétyl] glycérinate de méthyle
• N-[(butyrylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-[(butyrylthio) acetyl]-N-(3-chloro-2,6-diméthylphényl) alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(butyrylthio) acetyl] alaninate de méthyle
• N-[(butyrylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(isobutyrylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(Isobutyrylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(isobutyrylthio) acetyl] glycinate de méthyle
• N-[(isobutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(isobutyrylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(isobutyrylthio) acetyl] alaninate de méthyle
• N-[(isobutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(pentanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(pentonoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(pentanoylthio) acetyl] glycinate de méthyle
• N-[(pentanoyithio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(pentanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(pentanoylthio) acetyl] alaninate de méthyle
• N-[(pentanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(3-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(3-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-méthylbutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3-méthylbutyrylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(3-méthylbutyryltio) acetyl] alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-méthylbutyrylthio) acetyl] glycinate de méthyle
• N-[(2-méthylbutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphënyl)-N-[(2-méthylbutyrylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényi)-N-[(2-méthylbutyrylthio) acetyl] alaninate de méthyle
• N-[(2-méthylbutyrylthio) acetylj-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(3-méthylbutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2,2-diméthylpropionylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2,2-diméthylpropionylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2,2-diméthylpropionylthio) acetyl] glycinate de méthyle
• N-[(2,2-diméthylpropionylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2,2-diméthylpropionylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2,2-diméthylpropionylthio) acetyl] alaninate de méthyle
• N-[(2,2-diméthylpropionylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de de méthyle
• N-(2,6-diméthylphényl)-N-[(hexanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(hexanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(hexanoylthio) acetyl] glycinate de méthyle
• N-[(hexanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(hexanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(hexanoylthio) acetyl] alaninate de méthyle
• N-[(hexanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(3,3-diméthylbutyrylthio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3,3-diméthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(3,3-diméthylbutyrylthio) acetyl] glycinate de méthyle
• N-[(3,3-diméthylbutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3,3-diméthylbutyrylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(3,3-diméthylbutyrylthio) acetyl] alaninate de méthyle
• N-[(3,3-diméthylbutylthio)^. acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2-éthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-((2-éthylbutyrylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-éihylbutyrylthio) acetyl] glycinate de méthyle
• N-[(2-éthylbutyrylthio) acetylj-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-éthylbutyrylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-éthylbutyrylthio) acetyl] alaninate de méthyle
• N-[(2-éthylbutyrylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(heptanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(heptanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(heptanoylthio) acetyl] glycinate de méthyle
• N-[(heptanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(heptanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-I(heptanoylthio) acetyl] alaninate de méthyle
• N-[(heptanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2-éthylhexanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-éthylhexanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-éthylhexanoylthio) acetyl] glycinate de méthyle
• N-[(2-éthylhexanoylthio) acetyl]-N-(2,3,6-trimethylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-éthylhexanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-éthylhexanoylthio) acetyl] alaninate de méthyle
• N-[(2-éthylhexanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(octanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(octanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(octanoyithio) acetyl] glycinate de méthyle
• N-[(octanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(octanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(octanoylthio) acetyl] alaninate de méthyle
• N-[(octanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(nonanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényi)-N-[(nonanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(nonanoylthio) acetyl] glycinate de méthyle
• N-[(nonanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(nonanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(nonanoylthio) acetyl] alaninate de méthyle
• N-[(nonanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(décanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(décanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(décanoylthio) acetyl] glycinate de méthyle
• N-[(décanoyithio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(décanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(décanoylthio) acetyl] alaninate de méthyle
• N-[(décanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(undécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(undécanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(undécanoylthio) acetyl] glycinate de méthyle
• N-(2,3,6-triméthylphényl)-N-[(undécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(undécanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(undécanoylthio) acetyl] alaninate de méthyle
• N-(2,3,6-triméthylphényl)-N-[(undécanoylthio) acetyl] alaninate de méthyle
• N-(2,6-diméthyiphényl)-N-[(dodécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(dodécanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(dodécanoylthio) acetyl] glycinate de méthyle
• N-[(dodécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(dodécanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(dodécanoylthio) acetyl] alaninate de méthyle
• N-[(dodécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(tetradécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(tetradécanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(tetradécanoylthio) acetyl] glycinate de méthyle
• N-[(tetradécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(tetradécanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(tetradécanoylthio) acetyl] alaninate de méthyle
• N-[(tetradécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(hexadécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(hexadécanoytthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(hexadécanoylthio) acetyl] glycinate de méthyle
• N-[(hexadécanoylthio) acetyl]-N-(2,3,6 triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(hexadécanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(hexadécanoylthio) acetyl] alaninate de méthyle
• N-[(hexadécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(octadécanoylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-((octadécanoylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N([(octadécanoylthio) acetyl] glycinate de méthyle
• N-[(octadécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(octadécanoylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(octadécanoylthio) acetyl] alaninate de méthyle
• N-[(octadécanoylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(cyclohexanecarbonyithio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(cyclohexanecarbonylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(cyclohexanecarbonylthio) acetyl] glycinate de méthyle
• N-[(cyclohexanecarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphénylj-N-[(cyclohexylcarbonylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(cyclohexylcarbonylthio) acetyl] alaninate de méthyle
• N-[(cyclohexylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(cyclopentylcarbonylthio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(cyclopentylcarbonylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(cyclopentylcarbonylthio) acetyl] glycinate de méthyle
• N-[(cyclopentylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(cyclopentylcarbonylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(cyclopentylcarbonylthio) acetyl] alaninate de méthyle
• N-[(cyclopentylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(3,3-diméthylacryloylthio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3,3-diméthylacryloylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(3,3-diméthylacryloylthio) acetyl] glycinate de méthyle
• N-[(3,3-diméthylacryloyithio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(3,3-diméthylacryloylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2.6-diméthylphényl)-N-[(3,3-diméthylacryloylthio) acetyl] alaninate de méthyle
• N-[(3,3-diméthylacryloylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(benzoylthio) acetyl]-N-(2,6-diméthylphényl) glycinate de méthyle
• N-[(benzoylthio) acetyll-N-(3-chloro-2,6-diméthylphényi) glycinate de méthyle
• N-[(benzoylthio) acetyl]-N-(3-bromo-2,6-diméthylphényl) glycinate de méthyle
• N-[(benzoylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-[(benzoylthio) acetyl]-N-(3-chloro-2,6-diméthylphényl) alaninate de méthyle
• N-[(benzoylthio) acetyl]-N-(3-bromo-2,6-diméthylphényl) alaninate de méthyle
• N-[(benzoylthio] acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(methoxyacétylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(methoxyacéthylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(methoxyacétylthio) acetyl] glycinate de méthyle
• N-[(methoxyacétylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(méthoxyacétylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(methoxyacétylthio) acetyl] alaninate de méthyle
• N-[(methoxyacétylhio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2-furanylcarbonylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-furanylcarbonylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-furanylcarbonylthiuo) acetyl] glycinate de méthyle
• N-(2-furanylcarbonylthio) acetyl]-N-(2,3,S-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-furanylcarbonylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-furanylcarbonylthio) acetyl] alaninate de méthyle
• N-[(2-furanylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(2,6-diméthylphényl)-N-[(2-thienylcarbonylthio) acetyl] glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[(2-thienylcarbonylthio) acetyl] glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-thienylcarbonylthio) acetyl] glycinate de méthyle
• N-[(2-thienylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-[2-thienylcarbonylthio) acetyl] alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-[(2-thienylcarbonylthio) acetyl] alaninate de méthyle
• N-[(2-thienylcarbonylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-[(acetylthio) acetyl]-N-(3-chloro-2,6-diméthylphényl) glycinate de méthyle
• N-[(acetylthio) acetyl]-N-(3-bromo_-2,6-diméthylphényl) glycinate de méthyle
• N-[(acetylthio) acetyl]-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-[(acetylthio) acetyl]-N-(3-bromo-2,6-diméthylphényl) alaninate de méthyle
• N-[(acetylthio) acetyl]-N-(2,3,6-triméthylphényl) alaninate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-(mercaptoacetyl) glycinate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-(mercaptoacetyl) glycinate de méthyle
• N-(mercaptoacetyl)-N-(2,3,6-triméthylphényl) glycinate de méthyle
• N-(3-chloro-2,6-diméthylphényl)-N-(mercaptoacetyl) alaninate de méthyle
• N-(3-bromo-2,6-diméthylphényl)-N-(mercaptoacetyl) alaninate de méthyle
• N-(mercaptoacétyl)-N-(2,3,6-triméthylphényl) alaninate de méthyle
  
  
  
  
  
  
  
  
  
  
  

The following compounds can also be prepared in a manner similar to those described above:

• Methyl N- (2,6-dimethylphenyl) -N - [(propionylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyt) -N - [(propionylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(propionylthio) acetyl] glycinate
• Methyl N - [(propionylthioacetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(propionylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(propionylthio) acetyl] alaninate
• N - [(propionylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• N - [(butyrylthio) acetyl] -N- (2,6-dimethylphenyl) methyl glycinate
• N - [(butyrylthio) acetyll-N- (3-chloro-2,6-dimethylphenyl) methyl glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(butyrylthio) acetyl] glycerinate
• N - [(butyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• N - [(butyrylthio) acetyl] -N- (3-chloro-2,6-dimethylphenyl) methyl alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(butyrylthio) acetyl] alaninate
• N - [(butyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(isobutyrylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(Isobutyrylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(isobutyrylthio) acetyl] glycinate
• N - [(isobutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(isobutyrylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(isobutyrylthio) acetyl] alaninate
• N - [(isobutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(pentanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(pentonoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(pentanoylthio) acetyl] glycinate
• Methyl N - [(pentanoyithio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(pentanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(pentanoylthio) acetyl] alaninate
• N - [(pentanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(3-methylbutyrylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3-methylbutyrylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(3-methylbutyrylthio) acetyl] glycinate
• Methyl N- (3-methylbutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3-methylbutyrylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(3-methylbutyryltio) acetyl] alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2-methylbutyrylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-methylbutyrylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-methylbutyrylthio) acetyl] glycinate
• Methyl N - [(2-methylbutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-methylbutyrylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyi) -N - [(2-methylbutyrylthio) acetyl] alaninate
• N - [(2-methylbutyrylthio) acetylj-N- (2,3,6-trimethylphenyl) methyl alaninate
• N - [(3-methylbutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2,2-dimethylpropionylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2,2-dimethylpropionylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2,2-dimethylpropionylthio) acetyl] glycinate
• N - [(2,2-dimethylpropionylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2,2-dimethylpropionylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2,2-dimethylpropionylthio) acetyl] alaninate
• Methyl N - [(2,2-dimethylpropionylthio) acetyl] -N- (2,3,6-trimethylphenyl) alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(hexanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(hexanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(hexanoylthio) acetyl] glycinate
• Methyl N - [(hexanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(hexanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(hexanoylthio) acetyl] alaninate
• N - [(hexanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N - [(3,3-dimethylbutyrylthio) acetyl] -N- (2,6-dimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3,3-dimethylbutyrylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(3,3-dimethylbutyrylthio) acetyl] glycinate
• Methyl N - [(3,3-dimethylbutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3,3-dimethylbutyrylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(3,3-dimethylbutyrylthio) acetyl] alaninate
• N - [(3,3-dimethylbutylthio) ^. acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2-ethylbutyrylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - ((2-ethylbutyrylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-ethylbutyrylthio) acetyl] glycinate
• Methyl N - [(2-ethylbutyrylthio) acetylj-N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-ethylbutyrylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-ethylbutyrylthio) acetyl] alaninate
• N - [(2-ethylbutyrylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(heptanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(heptanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(heptanoylthio) acetyl] glycinate
• Methyl N - [(heptanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(heptanoylthio) acetyl] alaninate
• N- (3-bromo-2,6-dimethylphenyl) -NI (heptanoylthio) acetyl] methyl alaninate
• N - [(heptanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2-ethylhexanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-ethylhexanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-ethylhexanoylthio) acetyl] glycinate
• Methyl N - [(2-ethylhexanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-ethylhexanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-ethylhexanoylthio) acetyl] alaninate
• N - [(2-ethylhexanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(octanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(octanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(octanoyithio) acetyl] glycinate
• Methyl N - [(octanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(octanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(octanoylthio) acetyl] alaninate
• N - [(octanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(nonanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyi) -N - [(nonanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(nonanoylthio) acetyl] glycinate
• N - [(nonanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(nonanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(nonanoylthio) acetyl] alaninate
• N - [(nonanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(decanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(decanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(decanoylthio) acetyl] glycinate
• N - [(decanoyithio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(decanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(decanoylthio) acetyl] alaninate
• N - [(decanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(undecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(undecanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(undecanoylthio) acetyl] glycinate
• Methyl N- (2,3,6-trimethylphenyl) -N - [(undecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(undecanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(undecanoylthio) acetyl] alaninate
• Methyl N- (2,3,6-trimethylphenyl) -N - [(undecanoylthio) acetyl] alaninate
• Methyl N- (2,6-dimethyiphenyl) -N - [(dodecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(dodecanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(dodecanoylthio) acetyl] glycinate
• N - [(dodecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(dodecanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(dodecanoylthio) acetyl] alaninate
• N - [(dodecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(tetradecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(tetradecanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(tetradecanoylthio) acetyl] glycinate
• N - [(tetradecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(tetradecanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(tetradecanoylthio) acetyl] alaninate
• N - [(tetradecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(hexadecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(hexadecanoytthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(hexadecanoylthio) acetyl] glycinate
• N - [(hexadecanoylthio) acetyl] -N- (2,3,6 trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(hexadecanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(hexadecanoylthio) acetyl] alaninate
• N - [(hexadecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(octadecanoylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - ((octadecanoylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N ([(octadecanoylthio) acetyl] glycinate
• N - [(octadecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(octadecanoylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(octadecanoylthio) acetyl] alaninate
• N - [(octadecanoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N - [(cyclohexanecarbonyithio) acetyl] -N- (2,6-dimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(cyclohexanecarbonylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(cyclohexanecarbonylthio) acetyl] glycinate
• N - [(cyclohexanecarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenylj-N - [(cyclohexylcarbonylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(cyclohexylcarbonylthio) acetyl] alaninate
• N - [(cyclohexylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• N - [(cyclopentylcarbonylthio) acetyl] -N- (2,6-dimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(cyclopentylcarbonylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(cyclopentylcarbonylthio) acetyl] glycinate
• N - [(cyclopentylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(cyclopentylcarbonylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(cyclopentylcarbonylthio) acetyl] alaninate
• N - [(cyclopentylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N - [(3,3-dimethylacryloylthio) acetyl] -N- (2,6-dimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3,3-dimethylacryloylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(3,3-dimethylacryloylthio) acetyl] glycinate
• Methyl N - [(3,3-dimethylacryloyithio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(3,3-dimethylacryloylthio) acetyl] alaninate
• Methyl N- (3-bromo-2.6-dimethylphenyl) -N - [(3,3-dimethylacryloylthio) acetyl] alaninate
• N - [(3,3-dimethylacryloylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N - [(benzoylthio) acetyl] -N- (2,6-dimethylphenyl) glycinate
• N - [(benzoylthio) acetyll-N- (3-chloro-2,6-dimethylphenyi) methyl glycinate
• Methyl N - [(benzoylthio) acetyl] -N- (3-bromo-2,6-dimethylphenyl) glycinate
• N - [(benzoylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl glycinate
• N - [(benzoylthio) acetyl] -N- (3-chloro-2,6-dimethylphenyl) methyl alaninate
• N - [(benzoylthio) acetyl] -N- (3-bromo-2,6-dimethylphenyl) methyl alaninate
• N - [(benzoylthio] acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(methoxyacetylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(methoxyacethylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(methoxyacetylthio) acetyl] glycinate
• Methyl N - [(methoxyacetylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(methoxyacetylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(methoxyacetylthio) acetyl] alaninate
• N - [(methoxyacetylhio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2-furanylcarbonylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-furanylcarbonylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-furanylcarbonylthiuo) acetyl] glycinate
• N- (2-furanylcarbonylthio) acetyl] -N- (2,3, S-trimethylphenyl) methyl glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-furanylcarbonylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-furanylcarbonylthio) acetyl] alaninate
• N - [(2-furanylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (2,6-dimethylphenyl) -N - [(2-thienylcarbonylthio) acetyl] glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N - [(2-thienylcarbonylthio) acetyl] glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-thienylcarbonylthio) acetyl] glycinate
• Methyl N - [(2-thienylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N- [2-thienylcarbonylthio) acetyl] alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N - [(2-thienylcarbonylthio) acetyl] alaninate
• N - [(2-thienylcarbonylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• N - [(acetylthio) acetyl] -N- (3-chloro-2,6-dimethylphenyl) methyl glycinate
• Methyl N - [(acetylthio) acetyl] -N- (3-bromo _- 2,6-dimethylphenyl) glycinate
• Methyl N - [(acetylthio) acetyl] -N- (2,3,6-trimethylphenyl) glycinate
• N - [(acetylthio) acetyl] -N- (3-bromo-2,6-dimethylphenyl) methyl alaninate
• N - [(acetylthio) acetyl] -N- (2,3,6-trimethylphenyl) methyl alaninate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N- (mercaptoacetyl) glycinate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N- (mercaptoacetyl) glycinate
• Methyl N- (mercaptoacetyl) -N- (2,3,6-trimethylphenyl) glycinate
• Methyl N- (3-chloro-2,6-dimethylphenyl) -N- (mercaptoacetyl) alaninate
• Methyl N- (3-bromo-2,6-dimethylphenyl) -N- (mercaptoacetyl) alaninate
• N- (mercaptoacetyl) -N- (2,3,6-trimethylphenyl) methyl alaninate
  
  
  
  
  
  
  
  
  
  
  

Example 11 In vivo test on Plasmopara viticola on vine plants (preventive treatment)

• - 40 mg de matière active à tester
• - 40 cm³ d'eau
• - 0,2 cm³ de Tween 80 (agent tensioactif constitué d'un oléate de dérivé polyoxyéthyléné du sorbitol).

Vine plants (GAMAY grape variety). grown in pots are treated on both sides of their leaves by spraying with an aqueous solution or aqueous emulsion containing 1 mg / l of active ingredient to be tested; the sprayed solution or emulsion consists of:

• - 40 mg of active ingredient to be tested
• - 40 cm ³ of water
• - 0.2 cm ³ of Tween 80 (surfactant consisting of an oleate of polyoxyethylene derivative of sorbitol).

This solution thus formed is diluted with water to obtain solutions to be sprayed with concentrations of active ingredient to be tested of less than 1 mg / l.

After 48 hours, the contamination is carried out by spraying, on the underside of the leaves, an aqueous suspension of approximately 80,000 units / cm ³ of spores of the fungus. Then, the pots are placed for 48 hours in an incubation cell at 100% relative humidity and at 20 ° C.

The plants are checked 9 days after the infestation.

According to this test, all of the following compounds provided total protection when applied at the concentration of 0.11 g / I: 1 to 22, 24, 25, 29, 30, 33 to 36, 38 to 43, 45 , 47 to 53, 55, 65 to 68; all of the following compounds provided complete protection when applied at the concentration of 0.33 g / l: 44, 46, 56, 59, 62, 76, 81, 82, 84; all of the following compounds provided complete protection when applied at a concentration of 1 g / l: 23, 26 to 28, 32, 37, 54, 57, 60, 69 to 72, 78, 79, 83; at this same concentration of 1 g / l, good protection was obtained with compounds 58, 61 and 74, fairly good protection with compound 73 and average protection with compounds 63, 75, 77 and 80.

Among all these compounds, some (in particular compound n ° 1) still exhibit fairly good activity at much lower concentrations, even at concentrations of a few mg / l.

Example 12 In vivo test on Erysiphe graminis on barley (barley powdery mildew)

Barley, in pots, sown in loam, is treated at the 10 cm high stage by spraying with an aqueous solution or aqueous emulsion of the same composition as that described in Example 11 and with a concentration equal to 1 g / I. The test is repeated twice. After 48 hours, the barley plants are sprinkled with Erysiphe graminis spores, the dusting being carried out using diseased plants.

Reading is done 8 days after contamination.

Under these conditions, total protection of the barley plants is observed with compound No. 47, good protection with compound No. 6, and fairly good protection with compound No. 61.

Example 13 In vivo test on "Puccinia Striiformis responsible for wheat rust

Wheat, in pots, sown in loam, is treated at the 10 cm high stage by spraying with an aqueous solution or aqueous emulsion of the same composition as that described in Example 11 and with a concentration equal to 1 g / I. The test is repeated 2 times.

After 48 hours, an aqueous suspension of spores (50,000 sp / cm ³ ) is sprayed onto the wheat; this suspension was obtained from contaminated plants. The wheat is then placed for 48 hours in a climatic cell regulated as follows: illumination: 16 h / day; temperature: 20 ° C during the day and 15 ° C at night; relative humidity: 100%.

After these 2 days, the relative humidity is reduced to 60%. Seedlings state's control is the ^15th day after infection compared with the untreated control.

Under these conditions, a total protection of the wheat is observed with the compounds n ° 26 and 48 and a good protection with the compounds n ° 15, 17, 25, 28, 30, 43, 52, 57, 60, 61, 71, 77 .

Example 14 In vivo test on "Phytophthora Infestans responsible for tomato late blight

Tomato plants (Marmande variety) grown in a greenhouse and aged 60 to 75 days are treated by spraying with aqueous solutions or aqueous emulsions prepared as indicated in Example 11 and containing various concentrations of active ingredient to be tested.

After 48 hours, the treated plants are contaminated with an aqueous suspension of spores (zoosporangia) obtained from a culture of "Phytophthora Infestans" cultivated for 20 days on a medium based on chickpea flour.

The tomato plants are placed for 48 hours in an enclosure at a temperature of 16 to 18 ° C and provided with an atmosphere having a relative humidity of 100% then the relative humidity is then brought back to 80%.

The results are observed 8 days after contamination in a cell provided with an atmosphere having a relative humidity of 80%. The results are assessed by evaluation of the surface area of leaves invaded by the fungus and expressed by the “percentage of protection, that is to say 100 (1-S / Stm), S being the area invaded by the fungus on the considered plant and Stm being the surface invaded by the fungus on the untreated control plant. The results are indicated below, as in the previous examples, in the form of: total protection, good, fairly good or average.

Under these conditions and with an aqueous solution with a concentration of 1 g / l of active material to be tested, total protection was observed with the compounds no. 2, 3,12,14,15,19, 22, 23,31. 50, 52 and good protection with compounds n ° 17 and 45.

At the concentration of 0.11 g / 1, total protection was observed with compounds no. 16 and 66, good protection with compounds no. 24 and 38.

These experiments clearly illustrate the remarkable fungicidal properties of the compounds according to the invention, especially on fungi of the Phycomycete type (downy mildew) as well as their absence of phytotoxicity; their high activity at even low doses is quite remarkable. These compounds can therefore be used for the preventive and curative fight against fungal diseases (especially mildew) of plants or plants in general and, in particular of the vine, tobacco, hops, tomato, potato, sunflower and vegetable crops in general.

Furthermore, the compounds of the invention can also be applied against fungal diseases of other plants, in particular cereals, and more particularly wheat and barley.

For their practical use, the compounds according to the invention are rarely used alone. Most often they are part of compositions. These compositions, which can be used for the protection of plants against fungal diseases, contain as active material a compound according to the invention as described above in combination with solid or liquid carriers, acceptable in agriculture and surfactants also acceptable in agriculture . In particular, the usual inert supports and the usual surfactants can be used.

These compositions can also contain all kinds of other ingredients such as, for example, protective colloids, adhesives, thickeners, thixotropic agents, penetrating agents, stabilizers, sequestrants, etc. as well as other known active ingredients with pesticidal properties (in particular insecticides or fungicides) or with properties which promote plant growth (in particular fertilizers) or with properties which regulate plant growth. More generally, the compounds according to the invention can be combined with all the solid or liquid additives corresponding to the usual techniques of formulation.

The doses of use of the compounds according to the invention can vary within wide limits, in particular according to the virulence of the fungi and the climatic conditions.

In general, compositions containing 0.5 to 5000 ppm of active substance are very suitable; these values are indicated for the compositions ready for application. Ppm means "part per million •. The zone from 0.5 to 5000 ppm corresponds to a zone from 5 - 10 - ⁵ to 0.5% (weight percent).

As regards the compositions suitable for storage and transport, they more advantageously contain from 10 to 95% (by weight) of active substance.

Thus, the compositions for agricultural use according to the invention can contain the active materials according to the invention within very wide limits, ranging from 5 - 10 - ⁵ % to 95% (by weight).

According to what has already been said, the compounds according to the invention are generally associated with supports and optionally surfactants.

By the term "support .., in the present description, we mean an organic or mineral, natural or synthetic material, with which the active material is associated to facilitate its application on the plant, on seeds or on the soil. This support is therefore generally inert and it must be acceptable in agriculture, in particular on the treated plant. The support can be solid (clays, natural or synthetic silicates, silica, resins, waxes, solid fertilizers, etc.) or liquid (water, alcohols, ketones, petroleum fractions, aromatic or paraffinic hydrocarbons, chlorinated hydrocarbons, liquefied gases , etc ...).

The surfactant can be an emulsifying, dispersing or wetting agent, of ionic or nonionic type. Mention may be made, for example, of salts of polyacrylic acids, salts of lignosulfonic acids, salts of phenolsulfonic or naphthalene sulfonic acids, polycondensates of ethylene oxide on fatty alcohols or on fatty acids or on fatty amines , substituted phenols (in particular alkylphenols or arylphenols), ester salts of sulfosuccinic acids, taurine derivatives (in particular alkyltaurates), phosphoric esters of alcohols or of polyoxyethylated phenols. The presence of at least one surfactant is generally essential when the active material and / or the inert support are not soluble in water and the vector agent for the application is water.

For their application, the compounds of formula (I) are therefore generally in the form of compositions; these compositions according to the invention are themselves in fairly diverse forms, solid or liquid.

As forms of solid compositions, mention may be made of powders for dusting or dispersion (containing a compound of formula (I) up to 100%) and granules, in particular those obtained by extrusion, by compacting, by impregnation of a granulated support, by granulation from a powder (the content of compound of formula (1) in these granules being between 1 and 80% for the latter cases).

As forms of liquid compositions or intended to constitute liquid compositions during application, mention may be made of solutions, in particular water-soluble concentrates, emulsifiable concentrates, emulsions, concentrated suspensions, aerosols, powders wettable (or spraying powders), pasta.

The emulsifiable or soluble concentrates most often comprise 10 to 80% of active material, the emulsions or solutions ready for application containing, for their part, 0.01 to 20% of active material. In addition to the solvent, emulsifiable concentrates can contain, when necessary, 2 to 20% of suitable additives, such as stabilizers, surfactants, penetrating agents, corrosion inhibitors, dyes, adhesives. As an example, here is the composition of some concentrates:

According to another formula of emulsifiable concentrate, the following are used:

From these concentrates, emulsions with any desired concentration can be obtained by dilution with water, which are particularly suitable for application to the leaves.

The concentrated suspensions, also applicable in spraying, are prepared so as to obtain a stable fluid product which does not deposit and they usually contain from 10 to 75% of active material, from 0.5 to 15% of surfactants, from 0 , 1 to 10% of thixotropic agents, 0 to 10% of suitable additives, such as defoamers, corrosion inhibitors, stabilizers, penetrating agents and adhesives and, as support, water or an organic liquid in which the active ingredient is sparingly or not very soluble: certain organic solids or mineral salts can be dissolved in the support to help prevent sedimentation or as antifreeze for water.

Wettable powders (or spray powders) are usually prepared so that they contain 20 to 95% active ingredient, and they usually contain, in addition to the solid support, 0 to 5% of a wetting agent, 3 10% of a dispersing agent, and, when necessary, 0 to 10% of one or more stabilizers and / or other additives, such as penetrating agents, adhesives, or anti-caking agents, coloring agents, etc ...

As an example, here are various compositions of wettable powders:

Another 70% spray powder composition uses the following constituents:

Another 40% spray powder composition uses the following constituents:

Another 25% spray powder composition uses the following constituents:

Another 25% spray powder composition uses the following constituents:

Another 10% spray powder composition uses the following constituents:

To obtain these sprayable powders or wettable powders, the active materials are intimately mixed in appropriate mixers with the additional substances and ground with mills or other suitable grinders. This gives sprayable powders whose wettability and suspension are advantageous; they can be suspended with water at any desired concentration and this suspension can be used very advantageously in particular for application to the leaves of plants.

Instead of wettable powders, pasta can be made. The conditions and methods of making and using these pastes are similar to those of wettable powders or spraying powders.

As has already been said, aqueous dispersions and emulsions, for example compositions obtained by diluting with water a wettable powder or an emulsifiable concentrate according to the invention, are included in the general scope of the present invention. The emulsions can be of the water-in-oil or oil-in-water type and they can have a thick consistency like that of a "mayonnaise".

The granules intended to be placed on the ground are usually prepared so that they have dimensions of between 0.1 and 2 mm and they can be produced by agglomeration or impregnation. In general, the granules contain 0.5 to 25% of active material and 0 to 10% of additives such as stabilizers, slow release modifiers, binders and solvents.

According to an example of a granule composition, the following constituents are used:

In this particular case, the active material is mixed with epichlorohydrin and dissolved with 60 g of acetone; the polyethylene glycol and the cetyl ether of polyglycol are then added. The kaolin is sprayed with the solution obtained and it is then evaporated off in acetone under vacuum. Advantageously, such a microgranulate is used to combat soil fungi.

The compounds of formula (1) can also be used in the form of powders for dusting; one can also use a composition comprising 50 g of active material and 950 g of talc; one can also use a composition comprising 20 g of active material, 10 g of finely divided silica and 970 g of talc; these constituents are mixed and ground and the mixture is applied by dusting.

Claims (20)

1. A product, which can be used in particular as a pesticide, of the formula :

in which

R' and R⁵, which are identical or different, represent an alkyl or alkoxy radical having from 1 to ₄ carbon atoms or a halogen atom or the hydrogen atom, it being possible for only one of two radicals R' or R⁵ to have this last meaning,

R², R³ and R⁴, which are identical or different, represent the hydrogen atom or a halogen atom or an lakyl or alkoxy radical having from 1 to 4 carbon atoms,

R⁶ represents the hydrogen atom or a methyl radical,

R⁷ represents the hydrogen atom or an alkyl radical having from 1 to 12 carbon atoms or 1/n Mⁿ⁺, M being a cation of valency n and more particularly an ammonium cation (which is optionally substituted) or a metal cation, and

R⁶ represents the hydrogen atom or a radical of the formula R^9-CO-, in which R⁹ is an organic radical which represents '

- a linear or branched alkyl or alkenyl radical which has at most 18 carbon atoms and can be substituted by halogen atoms or hydroxyl, mercaptan, cyano or oxo groups or alkoxy, alkylthio, aryl, alkoxycarbonyl or acylamino radicals, these various radicals having at most 6 carbon atoms,

- a cycloalkyl radical which contains 3 to 7 carbon atoms in the ring and can be substituted by halogen atoms or alkyl groups having at most 4 carbon atoms,

- a phenyl or naphthyl radical which is optionally substituted by halogen atoms or alkyl, acyloxy, acyl or alkoxy groups, these various groups having at most 6 carbon atoms,

- a heterocyclic radical containing, in the ring, 5 or 6 atoms of which 1 to 3 are oxygen, nitrogen or sulphur hetero-atoms, it being possible for this heterocyclic radical to be substituted by chlorine atoms or methyl or ethyl groups, and the free valency of this radical R⁹ (i.e. the valency attached to the carbonyl group in the radical R^9--CO-) being by a carbon atom, or

- a radical comprising a heterocyclic group having the same meaning as that indicated in the preceding definition, this heterocyclic group being joined to the carbonyl group (of R^9--CO-) via a divalent methyle or ethylene radical.

2. A product according to claim 1, in which R⁷ represents an alkyl group having 1 to 12 carbon atoms and the halogen atoms are chlorine or bromine.

3. A product according to one of claims 1 or 2, in which

R² represents a hydrogen, chlorine or bromine atom,

R³ and R⁴ represent the hydrogen atom and

R' and R⁵ represent an alkyl group having from 1 to 4 carbon atoms.

4. A product according to one of claims 1 to 3 in which R⁹ represents

- an alkyl or alkenyl radical which is optionally substituted by chlorine substituted by chlorine atoms or alkoxy groups having from 1 to 4 carbon atoms or cyano, oxo, acetamido, phenyl, chlorophenyl, alkylthio or alkoxycarbonyl groups,

- a cyclopropyl, cyclopentyl or cyclohexyl radical,

- a phenyl radical which is optionally substituted by a chlorine or bromine atom, or

- a furyl, thienyl, trichlorothienyl or pyridyl radical.

5. A product according to one of claims 1 to 4, in which R^l, R⁵ and R⁷ are the methyl radical and R⁹ is an alkyl radical having from 1 to 9 carbon atoms.

6. A process for the preparation of a compound of the formula

which comprises reacting a N-phenyl-aminoacid derivative of the formula

with an acid chloride of the formula R⁹―CO―S―CH₂―CO―Cl (V), the symbols R¹ to R⁶ and R⁹ having the meanings given in one of claims 1 to 5 and the symbol R⁷ representing the hydrogen atom or an alkyl radical.

7. A process according to claim 6, wherein the reaction is carried out in an inert solvent at a temperature between 40 °C and the degradation temperature of the reactants and/or reaction products.

8. A process for the preparation of a product of the formula

which comprises reacting a N-phenyl-aminoacid derivative of the formula

with a thiocarboxylate derived from a thiocarboxylic acid of the formula R⁹CO―SH, in which formulae R' to R⁷ and R⁹ have the meanings given in one of claims 1 to 5.

9. A process according to claim 8, wherein the thiocarboxylate is an alkali metal thiocarboxylate or ammonium thiocarboxylate or alkaline earth metal thiocarboxylate and the reaction is carried out in an inert solvent at a temperature between 40 °C and the degradation temperature of the reactants and/or reaction products.

10. A process for the preparation of a product according to one of claims 1 to 5, of the formula :

which comprises reacting a compound of the formula :

with an alcohol.

11. A process according to claim 10, wherein the alcohol has the formula R⁷0H, R⁷ being an alkyl radical.

12. A process according to one of claims 10 or 11, wherein the alcohol is methanol.

13. A process according to one of claims 10 to 12, wherein the reaction is carried out in the presence of an alkali metal alcoholate, preferably sodium methanolate or potassium methanolate.

14. A process according to one of claims 10 to 12, wherein the reaction is carried out in the presence of a strong mineral or organic acid.

15. A process for the preparation of a product of the formula

which comprises reacting a mercaptan of the formula

with the chloride or anhydride of an acid of the formula R⁹―COOH, the symbols in these various formulae being such that R' to R⁷ and R⁹ have the meanings given in one of claims 1 to 5.

16. A process according to claim 15, wherein an acid chloride of the formula R⁹COCI is used and the reaction is carried out in an inert solvent in the presence of an acid acceptor.

17. A process according to claim 15, wherein an acid anhydride of the formula (R⁹CO)₂O, prepared in situ using the acid R⁹COOH and a dehydrating agent, is used.

18. A composition which can be used in particular for protecting plants against fungal diseases and which contains, as the active ingredient, a compound according to one of claims 1 to 5, in association with the customary inert carriers and, if appropriate, the customary surface-active agents.

19. A composition according to claim 18, which contains 5 10-5 to 95 % of active ingredient.

20. A process for combating fungal diseases in plants, wherein a composition according to one of claims 18 or 19 is used.